US3992533A - O-ethyl-S-N-propyl-O-(2-chloro-4-bromophenyl)-thiophosphate - Google Patents
O-ethyl-S-N-propyl-O-(2-chloro-4-bromophenyl)-thiophosphate Download PDFInfo
- Publication number
- US3992533A US3992533A US05/558,589 US55858975A US3992533A US 3992533 A US3992533 A US 3992533A US 55858975 A US55858975 A US 55858975A US 3992533 A US3992533 A US 3992533A
- Authority
- US
- United States
- Prior art keywords
- parts
- active ingredient
- compound
- formula
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004480 active ingredient Substances 0.000 claims description 29
- 150000001875 compounds Chemical class 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 12
- 229920000742 Cotton Polymers 0.000 claims description 4
- 241000238876 Acari Species 0.000 claims description 3
- 241000238631 Hexapoda Species 0.000 claims description 3
- 230000000361 pesticidal effect Effects 0.000 claims description 3
- 235000013311 vegetables Nutrition 0.000 claims description 3
- 108010022052 Proprotein Convertase 5 Proteins 0.000 claims 1
- 102100036365 Proprotein convertase subtilisin/kexin type 5 Human genes 0.000 claims 1
- 102100038950 Proprotein convertase subtilisin/kexin type 7 Human genes 0.000 claims 1
- 101710180647 Proprotein convertase subtilisin/kexin type 7 Proteins 0.000 claims 1
- 241000607479 Yersinia pestis Species 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- RYYWUUFWQRZTIU-UHFFFAOYSA-N Thiophosphoric acid Chemical compound OP(O)(S)=O RYYWUUFWQRZTIU-UHFFFAOYSA-N 0.000 abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 13
- 239000013543 active substance Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- -1 alkyl radical Chemical class 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000005995 Aluminium silicate Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 235000012211 aluminium silicate Nutrition 0.000 description 6
- 239000000969 carrier Substances 0.000 description 6
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 230000000895 acaricidal effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 235000008504 concentrate Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004495 emulsifiable concentrate Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 235000012222 talc Nutrition 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 235000013877 carbamide Nutrition 0.000 description 3
- 235000019993 champagne Nutrition 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 150000002191 fatty alcohols Chemical class 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 230000000749 insecticidal effect Effects 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241000994522 Anthrenus flavipes Species 0.000 description 2
- DRSHXJFUUPIBHX-UHFFFAOYSA-N COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 Chemical compound COc1ccc(cc1)N1N=CC2C=NC(Nc3cc(OC)c(OC)c(OCCCN4CCN(C)CC4)c3)=NC12 DRSHXJFUUPIBHX-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000219146 Gossypium Species 0.000 description 2
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- 241000043856 Necrobia rufipes Species 0.000 description 2
- 244000061176 Nicotiana tabacum Species 0.000 description 2
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 241000254112 Tribolium confusum Species 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 235000013601 eggs Nutrition 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 230000001473 noxious effect Effects 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006072 paste Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- 239000004563 wettable powder Substances 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- QQGRFMIMXPWKPM-UHFFFAOYSA-N 2,3,4-tributylphenol Chemical compound CCCCC1=CC=C(O)C(CCCC)=C1CCCC QQGRFMIMXPWKPM-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VIBJPUXLAKVICD-UHFFFAOYSA-N 4-bromo-2-chlorophenol Chemical compound OC1=CC=C(Br)C=C1Cl VIBJPUXLAKVICD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 241000254124 Aleyrodidae Species 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- 241001414896 Anthomyiidae Species 0.000 description 1
- 241001124076 Aphididae Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241001124134 Chrysomelidae Species 0.000 description 1
- 241000254171 Curculionidae Species 0.000 description 1
- 241000131287 Dermestidae Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PNKUSGQVOMIXLU-UHFFFAOYSA-N Formamidine Chemical class NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 description 1
- 241001454728 Gelechiidae Species 0.000 description 1
- 241001634830 Geometridae Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 240000002024 Gossypium herbaceum Species 0.000 description 1
- 235000004341 Gossypium herbaceum Nutrition 0.000 description 1
- 241000256244 Heliothis virescens Species 0.000 description 1
- 101001128694 Homo sapiens Neuroendocrine convertase 1 Proteins 0.000 description 1
- 101000601394 Homo sapiens Neuroendocrine convertase 2 Proteins 0.000 description 1
- 101001072067 Homo sapiens Proprotein convertase subtilisin/kexin type 4 Proteins 0.000 description 1
- 101000828971 Homo sapiens Signal peptidase complex subunit 3 Proteins 0.000 description 1
- 101000979222 Hydra vulgaris PC3-like endoprotease variant A Proteins 0.000 description 1
- 101000979221 Hydra vulgaris PC3-like endoprotease variant B Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010061217 Infestation Diseases 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 241001124557 Lymantriidae Species 0.000 description 1
- 241001190778 Lyonetiidae Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 102100032132 Neuroendocrine convertase 1 Human genes 0.000 description 1
- 102100037732 Neuroendocrine convertase 2 Human genes 0.000 description 1
- 241000220274 Nitidulidae Species 0.000 description 1
- 241000256259 Noctuidae Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 241000255964 Pieridae Species 0.000 description 1
- 241000500441 Plutellidae Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 102100036371 Proprotein convertase subtilisin/kexin type 4 Human genes 0.000 description 1
- 102100038946 Proprotein convertase subtilisin/kexin type 6 Human genes 0.000 description 1
- 101710180552 Proprotein convertase subtilisin/kexin type 6 Proteins 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 241001414857 Psyllidae Species 0.000 description 1
- 241000255893 Pyralidae Species 0.000 description 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 description 1
- 241000254107 Tenebrionidae Species 0.000 description 1
- 241001124685 Tenthredinidae Species 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 241001454295 Tetranychidae Species 0.000 description 1
- 241001454293 Tetranychus urticae Species 0.000 description 1
- 241000189579 Thripidae Species 0.000 description 1
- 241000255901 Tortricidae Species 0.000 description 1
- 235000009754 Vitis X bourquina Nutrition 0.000 description 1
- 235000012333 Vitis X labruscana Nutrition 0.000 description 1
- 240000006365 Vitis vinifera Species 0.000 description 1
- 235000014787 Vitis vinifera Nutrition 0.000 description 1
- 241001466336 Yponomeutidae Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 description 1
- QNXNOSDHDPYWME-UHFFFAOYSA-N [(2,4-dibromophenyl)-propoxy-lambda4-sulfanylidene]-ethoxy-dihydroxy-lambda5-phosphane Chemical compound C(C)OP(O)(O)=S(OCCC)C1=C(C=C(C=C1)Br)Br QNXNOSDHDPYWME-UHFFFAOYSA-N 0.000 description 1
- 239000000642 acaricide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- DNEHKUCSURWDGO-UHFFFAOYSA-N aluminum sodium Chemical compound [Na].[Al] DNEHKUCSURWDGO-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 239000001166 ammonium sulphate Substances 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- OOCMUZJPDXYRFD-UHFFFAOYSA-L calcium;2-dodecylbenzenesulfonate Chemical compound [Ca+2].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O.CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O OOCMUZJPDXYRFD-UHFFFAOYSA-L 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001055 chewing effect Effects 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- DYFIVHNTJCEYOT-UHFFFAOYSA-L disodium;1,2-dibutylnaphthalene;sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O.C1=CC=CC2=C(CCCC)C(CCCC)=CC=C21 DYFIVHNTJCEYOT-UHFFFAOYSA-L 0.000 description 1
- 239000004491 dispersible concentrate Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 235000005489 dwarf bean Nutrition 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 235000009973 maize Nutrition 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 229940032007 methylethyl ketone Drugs 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000003359 percent control normalization Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- KZOJQMWTKJDSQJ-UHFFFAOYSA-M sodium;2,3-dibutylnaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CCCC)C(CCCC)=CC2=C1 KZOJQMWTKJDSQJ-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 101150035983 str1 gene Proteins 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/14—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing aromatic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/16—Esters of thiophosphoric acids or thiophosphorous acids
- C07F9/165—Esters of thiophosphoric acids
- C07F9/18—Esters of thiophosphoric acids with hydroxyaryl compounds
Definitions
- This invention relates to the thiophosphoric acid phenylester of the formula ##SPC2##
- Another subject is the manufacture of the compound of the formula I and its use as active ingredient in pesticidal especially insecticidal preparations.
- the compound of formula I is most generally disclosed in French Pats. Nos. 1,295,613 and 1,567,444.
- a disclosure of even more closely related compounds -- such as e.g. the O-ethyl-S-n-propyl-O-(2,4-dichlorophenyl)- and O-ethyl-S-n-propyl-O-(2,4-dibromophenyl)-thiophosphoric acid ester -- is to be found in the U.S. Pat. No. 3,839,511. Accordingly the instant compound is a selection out of the latter U.S. Patent and shows surprisingly superior activities on at least the same toxicity level as the closest known compounds, especially with respect to its initial effect towards cotton pests.
- the new thiophosphoric acid phenylester may be prepared according to known processes such as: ##SPC3## ##SPC4## ##SPC5##
- Me represents an alkali metal, particularly sodium or potassium, ammonium or alkylammonium
- R stands for a C.sub. 1 -- C.sub. 4 alkyl radical, especially methyl or ethyl
- Hal is a halogen atom such as iodine especially however chlorine or bromine.
- acid binding agents there may be used tertiary amines, e.g. trialkylamines, pyridine or dialkylanilines; also suitable are inorganic bases such as hydrides, hydroxides, carbonates and bicarbonates of alkali and alkaline earth metals.
- inorganic bases such as hydrides, hydroxides, carbonates and bicarbonates of alkali and alkaline earth metals.
- a catalyst such as e.g. copper or copper chloride.
- the processes 1a to 3b are carried out at a reaction temperature between 0° and 130° C, at normal pressure and in solvents or diluents inert to the reactants.
- Suitable as inert solvents or diluents are for example ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, tetrahydrofurane; amides such as N,N-dialkylated carboxylic acid amides; aliphatic and aromatic hydrocarbons, which may be halogenated particularly benzene, toluene, xylene, chloroform, chlorobenzene; nitriles such as acetonitrile; DMSO.
- ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, tetrahydrofurane; amides such as N,N-dialkylated carboxylic acid amides; aliphatic and aromatic hydrocarbons, which may be halogenated particularly benzene, toluene, xylene, chloroform, chlorobenzene; nitrile
- the starting material of formula II can be made by methods analogous to those described for example in J. Org. Chem. 30, 3217 (1965).
- the compound of formula I has a broad insecticidal and acaricidal spectrum, the activity against plantpathogenic pests being emphasized.
- the compound acts above all as contact and congress poison and thus can be used for the control of all development stages such as eggs, larvae, nymphs, pupae and adults of sucking, chewing and boring pests and mites. Noxious individuals of this kind are to be found in the field of grape, soya, maize, tobacco, forest and stored products pests. Most valuable results however are achieved against pests noxious to cotton and vegetables.
- insecticidal and/or acaricidal effects can be substantially broadened and matched to given circumstances by the addition of other insecticides or acaricides.
- additional active ingredients may be selected from the group of organophosphorus compounds, nitrophenols and dervatives thereof, ureas, carbamates, chlorinated hydrocarbons, pyrethrinlike compounds and amidines especially formamidines a most valuable representative of which is 1,1-dimethyl-2-(2'-methyl-4'-chlorophenyl)-formamidine.
- the compound of formula I may be used as active substance alone or together with suitable carriers and/or additives.
- suitable carriers and additives may be solid or liquid and correspond to the substances conventionally used in formulation technique such, for example, as solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.
- the instant compound may be processed to conventionally formulated preparations as they are commonly used in application technology. They may be used as concentrates or dilutions according to the circumstances. Examples of such preparations are
- the above pesticidal preparations may be manufactured in known manner by intimately mixing and/or grinding the active ingredient with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substance.
- the active substance is mixed according to known methods with solid carriers.
- Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum silicates (feldspar and mica), calcium and magnesium suphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc.
- These substances can either be used alone or in admixture with one another. Also granular formulations can be easily manufactured according to known methods. To these mixtures may also be added stabilizers for the active ingredient and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents).
- Suitable additives are for example olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulfonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.
- cellulose derivatives methyl cellulose, carboxymethyl cellulose
- hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene
- the water-dispersible concentrates of the active substance are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substance and anti-foam agents (e.g. silicone oils) and, optionally solvents. Suitable additives are well known in the formulation technique and the manufacture of the concentrates is achieved by known methods.
- the active substance of formula I is dissolved in a suitable organic solvent, mixtures of solvents or in water. Such solvents are well known in the formulation technique.
- the content of active substance in the above described preparations is between 0.1% to 95% and most preferably between 2 and 50%.
- concentrations of up to 99.5% or even pure active substance are well known.
- the application rate of active ingredient on the other hand is as a rule about 0.1 to 2.0 kg per hectar.
- the active substance of formula I can, for example, be formulated as follows:
- the active ingredient is mixed with the carriers and ground.
- the active ingredient is mixed with epichlorohydrin and dissolved in 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on to kaolin, and the acetone subsequently evaporated in vacuo.
- the active ingredient is intimately mixed, in suitable mixers, with the additives, the mixture being then ground in an appropriate mill and roller. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.
- Emulsifiable concentrates are:
- Potted cotton and tobacco plants respectively were sprayed with 125 ppm of active ingredient in the form of an aqueous emulsion. After the coating had dried, the treated plants were infested with third instar larvae of Heliothis virescens. The tests were running under greenhouse conditions at24° C and 60% relative humitidy. Assessments to evaluate the initialeffect of the immediate acitivity of the active ingredient were carried out4, 24 and 48 hours after the infestation of the plants with the pests. Assessments to evaluate the initial effect of the activity over a prolonged period of the active ingredient were carried out as follows: thecoated test plants were infested with the test individuals 2 and 8 days respectively after the application of the active ingredient. Each test waschecked after 4, 24 and 48 hours. Test compounds
- Phaseolus vulgaris (dwarf beans) had an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test forthe acaricidal action.
- the occupying mobile stages were sprayed with the emulsified testing preparation from a chromatography atomiser so that the sprayed layer did not run off.
- the number of living and dead larvae, adults and eggs were evaluated after 7 days under a stereoscopic microscope and the result expressed in percentages.
- the treated plants were kept in greenhouse compartments at 25° C. The evaluation of the test proved good activity of the active ingredient.
- a dust on a base of talcum and containing 5% active ingredient was applied to filter paper in concentrations of 100, 50, 25, 12.5 6.2 and 3.1 mg of active substance per m.sup. 2.
- Onto each of the treated substrates were applied 5 Necrobia rufipes, Rhyzoperta dominica, Anthrenus vorax and Tribolium confusum individuals respectively. Evaluation took place 24 hours later. Test compounds were same as set forth in Example 2.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Dentistry (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Biochemistry (AREA)
- Molecular Biology (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The thiophosphoric acid phenylester of the formula ITS MANUFACTURE AND USE IN PEST CONTROL IS DISCLOSED.
Description
This is a continuation in part of application Ser. No. 429,425 filed Dec. 28, 1973 which itself is a continuation of application Ser. No. 295,407 filed Oct. 5, 1972, both now abandoned.
This invention relates to the thiophosphoric acid phenylester of the formula ##SPC2##
Another subject is the manufacture of the compound of the formula I and its use as active ingredient in pesticidal especially insecticidal preparations.
The compound of formula I is most generally disclosed in French Pats. Nos. 1,295,613 and 1,567,444. A disclosure of even more closely related compounds -- such as e.g. the O-ethyl-S-n-propyl-O-(2,4-dichlorophenyl)- and O-ethyl-S-n-propyl-O-(2,4-dibromophenyl)-thiophosphoric acid ester -- is to be found in the U.S. Pat. No. 3,839,511. Accordingly the instant compound is a selection out of the latter U.S. Patent and shows surprisingly superior activities on at least the same toxicity level as the closest known compounds, especially with respect to its initial effect towards cotton pests.
The new thiophosphoric acid phenylester may be prepared according to known processes such as: ##SPC3## ##SPC4## ##SPC5##
In the above formulae Me represents an alkali metal, particularly sodium or potassium, ammonium or alkylammonium, R stands for a C.sub. 1 -- C.sub. 4 alkyl radical, especially methyl or ethyl and Hal is a halogen atom such as iodine especially however chlorine or bromine.
As acid binding agents there may be used tertiary amines, e.g. trialkylamines, pyridine or dialkylanilines; also suitable are inorganic bases such as hydrides, hydroxides, carbonates and bicarbonates of alkali and alkaline earth metals. Depending on the reaction conditions it may be desirable in order to enhance the yield or reduce the duration of the reaction to use a catalyst such as e.g. copper or copper chloride. The processes 1a to 3b are carried out at a reaction temperature between 0° and 130° C, at normal pressure and in solvents or diluents inert to the reactants. Suitable as inert solvents or diluents are for example ethers and ethereal compounds such as diethyl ether, dipropyl ether, dioxane, tetrahydrofurane; amides such as N,N-dialkylated carboxylic acid amides; aliphatic and aromatic hydrocarbons, which may be halogenated particularly benzene, toluene, xylene, chloroform, chlorobenzene; nitriles such as acetonitrile; DMSO. For processes 3a and 3b alcohols such as ethanol, n-propanol or isopropanol are also suitable.
The starting material of formula II can be made by methods analogous to those described for example in J. Org. Chem. 30, 3217 (1965).
The compound of formula I has a broad insecticidal and acaricidal spectrum, the activity against plantpathogenic pests being emphasized. The compound acts above all as contact and stomac poison and thus can be used for the control of all development stages such as eggs, larvae, nymphs, pupae and adults of sucking, chewing and boring pests and mites. Noxious individuals of this kind are to be found in the field of grape, soya, maize, tobacco, forest and stored products pests. Most valuable results however are achieved against pests noxious to cotton and vegetables. In this connection the following families of insects and acarina must be considered: Chrysomelidae, Curculionidae, Dermestidae, Nitidulidae, Tenebrionidae; Anthomyiidae; Aleyrodidae, Aphididae, Psyllidae; Tenthredinidae; Gelechiidae, Geometridae, Hyponomeutidae, Lymantriidae, Lyonetiidae, Noctuidae, Olethreutidae, Phaloniidae, Pieridae, Plutellidae, Pyralidae, Tortricidae; Thripidae; Tetranychidae. The insecticidal and/or acaricidal effects can be substantially broadened and matched to given circumstances by the addition of other insecticides or acaricides. Such additional active ingredients may be selected from the group of organophosphorus compounds, nitrophenols and dervatives thereof, ureas, carbamates, chlorinated hydrocarbons, pyrethrinlike compounds and amidines especially formamidines a most valuable representative of which is 1,1-dimethyl-2-(2'-methyl-4'-chlorophenyl)-formamidine.
The compound of formula I may be used as active substance alone or together with suitable carriers and/or additives. Suitable carriers and additives may be solid or liquid and correspond to the substances conventionally used in formulation technique such, for example, as solvents, dispersants, wetting agents, adhesives, thickeners, binders and/or fertilisers.
For application the instant compound may be processed to conventionally formulated preparations as they are commonly used in application technology. They may be used as concentrates or dilutions according to the circumstances. Examples of such preparations are
______________________________________ in solid form: dusts, scattering agents or granules; in liquid form: a) concentrates of active ingredient dispersible in water: wettable powders, pastes or emulsifiable concen- trates; b) solutions ______________________________________
The above pesticidal preparations may be manufactured in known manner by intimately mixing and/or grinding the active ingredient with the suitable carriers, optionally with the addition of dispersants or solvents which are inert towards the active substance. To manufacture dusts and scattering agents, the active substance is mixed according to known methods with solid carriers. Suitable carriers are, for example: kaolin, talcum, bolus, loess, chalk, limestone, ground limestone, attaclay, dolomite, diatomaceous earth, precipitated silica, alkaline earth silicates, sodium and potassium aluminum silicates (feldspar and mica), calcium and magnesium suphates, magnesium oxide, ground synthetic materials, fertilisers, for example ammonium sulphate, ammonium phosphate, ammonium nitrate, urea, ground vegetable products, such as corn meal, bark dust, sawdust, nutshell meal, cellulose powder, residues of plant extractions, activated charcoal etc.
These substances can either be used alone or in admixture with one another. Also granular formulations can be easily manufactured according to known methods. To these mixtures may also be added stabilizers for the active ingredient and/or non-ionic, anionic and cationic surface active substances, which for example improve the adhesion of the active ingredients on plants or parts of plants (adhesives and agglutinants) and/or ensure a better wettability (wetting agents) and dispersibility (dispersing agents). Suitable additives are for example olein/chalk mixture, cellulose derivatives (methyl cellulose, carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl and dialkyl phenols having 5 to 15 ethylene oxide radicals per molecule and 8 to 9 carbon atoms in the alkyl radical, lignin sulfonic acids, their alkali metal and alkaline earth metal salts, polyethylene glycol ethers (carbowaxes), fatty alcohol polyethylene glycol ethers having 5 to 20 ethylene oxide radicals per molecule and 8 to 18 carbon atoms in the fatty alcohol moiety, condensation products of ethylene oxide/propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols, condensation products of urea and formaldehyde, and also latex products.
The water-dispersible concentrates of the active substance, i.e. wettable powders, pastes and emulsifiable concentrates, are agents which can be diluted with water to any concentration desired. They consist of active substance, carrier, optionally additives which stabilize the active substance, surface-active substance and anti-foam agents (e.g. silicone oils) and, optionally solvents. Suitable additives are well known in the formulation technique and the manufacture of the concentrates is achieved by known methods.
For the preparation of solutions the active substance of formula I is dissolved in a suitable organic solvent, mixtures of solvents or in water. Such solvents are well known in the formulation technique. The content of active substance in the above described preparations is between 0.1% to 95% and most preferably between 2 and 50%. In this connection it should be mentioned that if the application is carried out from an aircraft or with some other suitable means, it is possible to use concentrations of up to 99.5% or even pure active substance. The application rate of active ingredient on the other hand is as a rule about 0.1 to 2.0 kg per hectar. The active substance of formula I can, for example, be formulated as follows:
The following substances are used to manufacture a) a 5% and b) a 2% dust:
______________________________________ a) 5 parts of active ingredient 95 parts of talcum b) 2 parts of active ingredient 1 part of highly disperse silica 97 parts of talcum. ______________________________________
The active ingredient is mixed with the carriers and ground.
The following substances are used to produce 5% granules:
5 parts of active ingredient
0.25 parts of epichlorohydrin
0.25 parts of cetyl polyglycol ether
3.50 parts of polyethylene glycol
91 parts of kaolin (particle size 0.3-0.8 mm).
The active ingredient is mixed with epichlorohydrin and dissolved in 6 parts of acetone; the polyethylene glycol and cetyl polyglycol ether are then added. The thus obtained solution is sprayed on to kaolin, and the acetone subsequently evaporated in vacuo.
The following constituents are used for the preparation of (a) a 40%, (b) and (c) a 25% and (d) a 10% wettable powder:
______________________________________ a) 40 parts of active ingredient 5 parts of sodium lignin sulphonate 1 part of sodium dibutyl-naphthalene sulphonate 54 parts of silica acid. b) 25 parts of active ingredient 4.5 parts of calcium lignin sulphonate 1.9 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1) 1.5 parts of sodium dibutyl naphthalene sulphate 19.5 parts of silica acid 19.5 parts of Champagne chalk 28.1 parts of kaolin. c) 25 parts of active ingredient 2.5 parts of isooctylphenoxy-polyoxyethylene-ethanol 1.7 parts of Champagne chalk/hydroxyethyl cellulose mixture (1:1) - 8.3 parts of sodium aluminum silicate 16.5 parts of kieselgur 46 parts of kaolin d) 10 parts of active ingredient 3 parts of a mixture of the sodium salts of saturated fatty alcohol sulfates 5 parts of naphthalenesulphonic acid/formaldehyde condensate 82 parts of kaolin. ______________________________________
The active ingredient is intimately mixed, in suitable mixers, with the additives, the mixture being then ground in an appropriate mill and roller. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.
The following substances are used to produce (a) a 10% (b) a 25% and (c) a 50% emulsifiable concentrate:
______________________________________ a) 10 parts of active ingredient 3.4 parts of epoxidised vegetable oil 3.4 parts of a combination emulsifier consisting of fatty alcohol polyglycol ether and alkylarylsul- phonate calcium salt 40 parts of dimethylformamide 43.2 parts of xylene. b) 25 parts of active ingredient 2.5 parts of epoxidised vegetable oil 10 parts of an alkylarylsulphonate/fatty alcohol- polyglycol ether mixture 5 parts of dimethylformamide 57.5 parts of xylene. c) 50 parts of active ingredient 4.2 parts of tributylphenol polyglycolic ether 5.8 parts of calcium dodecylbenzenesulfonate 20 parts of cyclohexanone 20 parts of xylene ______________________________________
From these concentrates it is possible to produce, by dilution with water, emulsions of any desired concentration.
The following substances are used to manufacture (a) a 5% and (b) a 95% spray:
______________________________________ a) 5 parts of active ingredient 1 part of epichlorohydrin 94 parts of petrol (boiling range 160-190° C) b) 95 parts of active ingredient 5 parts of epichlorohydrin ______________________________________
The following examples illustrate the manufacture and testing of the compound according to the present invention.
a. 31.1 g (0.15 mole) 2-chloro-4-bromophenol were dissolved in 150 ml benzene and 15.1 g triethylamine were then added. At 10-15° C, 32.0g of 0-ethyl-S-n-propyl-chlorothiophosphate were added dropwise with continuous stirring. Stirring was then continued for 12 hours at room temperature. The mixture was washed with water, 3% Na.sub. 2 CO.sub. 3 solution and water and dried over anhydrous sodium sulphate. The benzene was distilled off and the residue purified by distillation (at 130°C/0.01 torr). Yield: 49 g; refractive index nD.sup. 20 1.5466.
b. 71.8 g 0,0-diethyl-0(2-chloro-4-bromophenyl)-phosphorothioate were dissolved in an ethanolic solution of KSH (consisting of 9.5 g H2 S; 13.5 g KOH, and 120 ml ethanol) and boiled for 10 hours under reflux. The solvent was then distilled off and the residue dissolved in 1000 ml water whereupon the waterinsoluble portion was extracted with toluene. The aqueous layer was separated and mixed with 30 g n-propyl-bromide in 8 g methyl-ethyl-ketone. This mixture was kept for 6 hours at 70° to 77° C, then cooled and the oily reaction product separated and dried. Yield: 71 g; refractive index: nD.sup. 20 1.5466.
Potted cotton and tobacco plants respectively were sprayed with 125 ppm of active ingredient in the form of an aqueous emulsion. After the coating had dried, the treated plants were infested with third instar larvae of Heliothis virescens. The tests were running under greenhouse conditions at24° C and 60% relative humitidy. Assessments to evaluate the initialeffect of the immediate acitivity of the active ingredient were carried out4, 24 and 48 hours after the infestation of the plants with the pests. Assessments to evaluate the initial effect of the activity over a prolonged period of the active ingredient were carried out as follows: thecoated test plants were infested with the test individuals 2 and 8 days respectively after the application of the active ingredient. Each test waschecked after 4, 24 and 48 hours. Test compounds
__________________________________________________________________________ ##STR1##
__________________________________________________________________________ I II III X Br Cl Br Y Cl Cl Br Expl. 1 Comp.26 Comp.29 US 3,839,511 US 3,839,511 toxicity 400- 400 300 mg/kg rat 900 per Os __________________________________________________________________________ % mortality Time of compound I compound II compound III Assessment residual residual residual in hours initial 2d 8d initial 2d 8d initial 2d 8d __________________________________________________________________________ 4 100 100 50 80 50 30 75 30 0 24 100 100 100 90 100 50 100 100 5 48 100 100 100 100 100 100 100 100 55 __________________________________________________________________________
Phaseolus vulgaris (dwarf beans) had an infested piece of leaf from a mass culture of Tetranychus urticae placed on them 12 hours before the test forthe acaricidal action. The occupying mobile stages were sprayed with the emulsified testing preparation from a chromatography atomiser so that the sprayed layer did not run off. The number of living and dead larvae, adults and eggs were evaluated after 7 days under a stereoscopic microscope and the result expressed in percentages. During the "interim", the treated plants were kept in greenhouse compartments at 25° C. The evaluation of the test proved good activity of the active ingredient.
A dust on a base of talcum and containing 5% active ingredient was applied to filter paper in concentrations of 100, 50, 25, 12.5 6.2 and 3.1 mg of active substance per m.sup. 2. Onto each of the treated substrates were applied 5 Necrobia rufipes, Rhyzoperta dominica, Anthrenus vorax and Tribolium confusum individuals respectively. Evaluation took place 24 hours later. Test compounds were same as set forth in Example 2.
______________________________________ Dosage needed (mg a.i./m.sup.2) which provides a 100% control within 24 hours Test Animal compound I compound II compound III ______________________________________ Necrobia rufipes 3.1 6.2 6.2 Tribolium confusum 50 100 >100 Rhyzoperta dominica 25 50 100 Anthrenus vorax 25 50 100 ______________________________________
Claims (4)
1. A pesticidal composition which comprises as active ingredient the compound of the formula ##SPC6##
and a carrier.
2. The compound of the formula ##SPC7##
3. A method of controlling harmful insects and representatives of the order acarina which comprises applying thereto a pesticidally effective amount of the compound of the formula ##SPC8##
4. A method according to claim 3 which comprises controlling insects harmful to cotton and vegetables.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US05/558,589 US3992533A (en) | 1971-10-12 | 1975-03-14 | O-ethyl-S-N-propyl-O-(2-chloro-4-bromophenyl)-thiophosphate |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CH14855/71 | 1971-10-12 | ||
CH1485571A CH570762A5 (en) | 1971-10-12 | 1971-10-12 | O-ethyl-s-propyl-o-(halophenyl) thiophosphates - with insecticidal and acaricidal activity |
US42942573A | 1973-12-28 | 1973-12-28 | |
US05/558,589 US3992533A (en) | 1971-10-12 | 1975-03-14 | O-ethyl-S-N-propyl-O-(2-chloro-4-bromophenyl)-thiophosphate |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US42942573A Continuation-In-Part | 1971-10-12 | 1973-12-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3992533A true US3992533A (en) | 1976-11-16 |
Family
ID=27177244
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/558,589 Expired - Lifetime US3992533A (en) | 1971-10-12 | 1975-03-14 | O-ethyl-S-N-propyl-O-(2-chloro-4-bromophenyl)-thiophosphate |
Country Status (1)
Country | Link |
---|---|
US (1) | US3992533A (en) |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4223026A (en) * | 1979-03-23 | 1980-09-16 | The Dow Chemical Company | Insecticidal synergistic mixture of O,O-diethyl O-(3,5,6-trichloro-2-pyridinyl)phosphorothioate and O-ethyl O-(2-chloro-4-bromophenyl)-S-n-propyl phosphorothioate |
US4609649A (en) * | 1984-07-31 | 1986-09-02 | Ciba-Geigy Corporation | Pesticidal compositions employing a synergistic combination of endosulfan and profenofos |
US20030100604A1 (en) * | 2000-03-28 | 2003-05-29 | Reiner Fischer | Active substance combinations having insecticidal and acaricidal properties |
US7060692B2 (en) | 2000-08-31 | 2006-06-13 | Bayer Cropscience Ag | Active ingredient combinations comprising insecticidal and acaricidal properties |
CN103621551A (en) * | 2012-08-27 | 2014-03-12 | 南京华洲药业有限公司 | Composite insecticidal composition containing thiamethoxam and profenofos, and use thereof |
CN103651542A (en) * | 2012-09-04 | 2014-03-26 | 南京华洲药业有限公司 | Composite insecticidal composition containing ethiprole and profenofos and application of composite insecticidal composition |
US8846567B2 (en) | 2009-03-25 | 2014-09-30 | Bayer Cropscience Ag | Active compound combinations having insecticidal and acaricidal properties |
WO2020049493A1 (en) | 2018-09-06 | 2020-03-12 | Pi Industries Ltd. | Stable agrochemical composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3530206A (en) * | 1966-03-25 | 1970-09-22 | Ciba Ltd | O,o-diloweralkyl-o - (2-chloro - 4 - bromo phenyl) phosphates and thiophosphates |
US3839511A (en) * | 1970-12-26 | 1974-10-01 | Bayer Ag | O-ethyl-s-n-propyl-o-(substituted phenyl)-phosphorothiolates |
-
1975
- 1975-03-14 US US05/558,589 patent/US3992533A/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3530206A (en) * | 1966-03-25 | 1970-09-22 | Ciba Ltd | O,o-diloweralkyl-o - (2-chloro - 4 - bromo phenyl) phosphates and thiophosphates |
US3839511A (en) * | 1970-12-26 | 1974-10-01 | Bayer Ag | O-ethyl-s-n-propyl-o-(substituted phenyl)-phosphorothiolates |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4223026A (en) * | 1979-03-23 | 1980-09-16 | The Dow Chemical Company | Insecticidal synergistic mixture of O,O-diethyl O-(3,5,6-trichloro-2-pyridinyl)phosphorothioate and O-ethyl O-(2-chloro-4-bromophenyl)-S-n-propyl phosphorothioate |
US4609649A (en) * | 1984-07-31 | 1986-09-02 | Ciba-Geigy Corporation | Pesticidal compositions employing a synergistic combination of endosulfan and profenofos |
US20030100604A1 (en) * | 2000-03-28 | 2003-05-29 | Reiner Fischer | Active substance combinations having insecticidal and acaricidal properties |
US6900190B2 (en) | 2000-03-28 | 2005-05-31 | Bayer Aktiengesellschaft | Active substance combinations having insecticidal and acaricidal properties |
US7060692B2 (en) | 2000-08-31 | 2006-06-13 | Bayer Cropscience Ag | Active ingredient combinations comprising insecticidal and acaricidal properties |
US8846567B2 (en) | 2009-03-25 | 2014-09-30 | Bayer Cropscience Ag | Active compound combinations having insecticidal and acaricidal properties |
CN103621551A (en) * | 2012-08-27 | 2014-03-12 | 南京华洲药业有限公司 | Composite insecticidal composition containing thiamethoxam and profenofos, and use thereof |
CN103651542A (en) * | 2012-09-04 | 2014-03-26 | 南京华洲药业有限公司 | Composite insecticidal composition containing ethiprole and profenofos and application of composite insecticidal composition |
WO2020049493A1 (en) | 2018-09-06 | 2020-03-12 | Pi Industries Ltd. | Stable agrochemical composition |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3987102A (en) | Phenoxy (benzyloxy) benzene derivatives | |
US4153731A (en) | Phenoxy (benzyloxy/benzylthio) benzene derivatives | |
US3992533A (en) | O-ethyl-S-N-propyl-O-(2-chloro-4-bromophenyl)-thiophosphate | |
US4130655A (en) | Pesticidal 2,2-dimethyl-3-isobutyl-cyclopropionates | |
US3839509A (en) | O-alkyl-s-alkyl-o-substituted phenylthiophosphoric acid esters | |
US3987108A (en) | Benzyl (benzyloxy) benzene derivatives | |
GB1570928A (en) | Pesticidal cyclopropane carboxylic acid esters | |
CA1100991A (en) | Esters | |
CA1142541A (en) | Esters | |
US4072752A (en) | Pesticidal benzaspiro carboxylates | |
US4094989A (en) | Methylenedioxy substituted benzene derivatives | |
US4000314A (en) | Pesticidal N-(2,2-dicyanovinyl)-N-benzyl-anilines | |
US4098902A (en) | 1-phenyl-1,3,5,7-tetraaza-4-sulpha-hept-1-en-6-one derivatives | |
US3982015A (en) | N-propargyl-anilinomethylenemalodinitrile derivatives | |
US4115583A (en) | Pesticidal sulphenylated formamidine compounds | |
US3962316A (en) | Carbamate | |
US3939274A (en) | Phenoxyphenylalkanoic acid ester insecticides | |
CA1080743A (en) | Spiroheptenyl carboxylate | |
US4064263A (en) | 4,5-Benzospiro(2,4)-heptane (and hepta-4,6-diene)-1-carboxylic acid esters and compositions containing same | |
CA1047521A (en) | Thiolphosphoric acid esters | |
CA1092145A (en) | Pesticidal metaphenoxybenzylcyclopropane carboxylate derivatives | |
US4017640A (en) | 1-P-Alkylphenyl-1-p-(alkoxyphenyl)-2-nitroalkanes | |
US3973014A (en) | Thiolphosphoric acid ester insecticide | |
IL40476A (en) | O,s-dialkyl-o-phenyl thiophosphoric acid esters,their manufacture and their use in pest control | |
US3920771A (en) | O-ethyl-s-(n)-propyl-s-carbamoylalkyl dithiophosphates |